U.S. patent application number 10/491268 was filed with the patent office on 2004-09-30 for preparation of oligomeric cyclocarbonates and their use in ionisocyanate or hybrid nonisocyanate polyurethanes.
Invention is credited to Figovsky, Oleg, Shapovalov, Leonid.
Application Number | 20040192803 10/491268 |
Document ID | / |
Family ID | 23268392 |
Filed Date | 2004-09-30 |
United States Patent
Application |
20040192803 |
Kind Code |
A1 |
Figovsky, Oleg ; et
al. |
September 30, 2004 |
Preparation of oligomeric cyclocarbonates and their use in
ionisocyanate or hybrid nonisocyanate polyurethanes
Abstract
A method and apparatus for synthesis of oligomeric
cyclocarbonates from epoxy compounds and carbon dioxide in the
presence of a catalyst. Star epoxy compounds and their preparation
and use in making star cyclocarbonates, star hydroxy urethane
oligomers, and star NIPU and HNIPU. Acrylic epoxy compounds,
acrylic cyclocarbonates, acrylic hydroxy urethane oligomers, and
acrylic NIPU and HNIPU and their methods of preparation.
Inventors: |
Figovsky, Oleg; (Haifa,
IL) ; Shapovalov, Leonid; (Haifa, IL) |
Correspondence
Address: |
KIRSCHSTEIN, OTTINGER, ISRAEL
& SCHIFFMILLER, P.C.
489 FIFTH AVENUE
NEW YORK
NY
10017
|
Family ID: |
23268392 |
Appl. No.: |
10/491268 |
Filed: |
March 29, 2004 |
PCT Filed: |
October 1, 2002 |
PCT NO: |
PCT/US02/31120 |
Current U.S.
Class: |
521/178 ;
528/421 |
Current CPC
Class: |
C08L 2666/02 20130101;
C08L 63/00 20130101; C08G 71/04 20130101; C08L 63/00 20130101; C08L
75/04 20130101; C08L 63/00 20130101; C07D 303/32 20130101; C08G
59/1405 20130101 |
Class at
Publication: |
521/178 ;
528/421 |
International
Class: |
C07D 321/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 1, 2001 |
US |
60325562 |
Claims
1-61: (Canceled)
62: An improved method of synthesizing a cyclocarbonate from an
epoxy compound and carbon dioxide at low pressure and temperature
in a reactor, the method comprising the steps of: a) supplying a
catalyst to the reactor; b) introducing the epoxy compound to the
catalyst-containing reactor to create a reactionary mass in the
reactor; and c) feeding carbon dioxide to the reactor through a
turbine mixing device and a gas entrainment impeller directly into
the reactionary mass, the reactionary mass being saturated with the
carbon dioxide and reacting to form the cyclocarbonate.
63: The method of claim 62, wherein the epoxy compound is selected
from the group consisting of aromatic epoxies, aliphatic epoxies,
cycloaliphatic epoxies and acrylic epoxies.
64: The method of claim 62, wherein the epoxy compound is a star
epoxy compound.
65: The method of claim 64, wherein the star epoxy compound has a
functionality of about 3 or greater.
66: The method of claim 62, wherein the epoxy compound is an
acrylic polymer with pendant epoxy groups.
67: An apparatus for producing cyclocarbonates from epoxy compounds
and carbon dioxide at reduced pressure, time, and temperature, the
apparatus comprising: a) a reactor vessel having inlets for
supplying a catalyst and the epoxy compounds thereto and for
supplying the carbon dioxide thereto, wherein the catalyst and
epoxy compound form a reactionary mass; and b) a turbine mixing
device located in the reactor vessel, the turbine mixing device
comprising a hollow shaft containing an inlet port, said shaft
being in fluid communication with an impeller containing an outlet
through which the carbon dioxide flows and is introduced into the
reactionary mass.
68: A star oligomer selected from the group consisting of star
epoxy oligomers, star cyclocarbonate oligomers, star
hydroxyurethane oligomers and star aminonydroxyurethane
oligomers.
69: The star oligomer of claim 68, wherein said oligomer has a
functionality greater than 2.
70: The star hydroxyurethane oligomer according to claim 68,
wherein the oligomer comprises at least one hydroxyurethane
linkage.
71: The star aminohydroxyurethane oligomer according to claim 68,
wherein the oligomer comprises at least one hydroxyurethane
linkage.
72: A star nonisocyanate network polyurethane.
73: The star nonisocyanate network polyurethane of claim 72,
wherein the network polyurethane comprises a star cyclocarbonate
cross-linked with a bi-functional amine having a functionality of
at least about 2.
74: The star nonisocyanate network polyurethane of claim 72,
wherein the network polyurethane is in the form of a foam or a UV
stable coating.
75: A paint or coating composition containing the star
nonisocyanate network polyurethane of claim 72.
76: A method of synthesizing a star nonisocyanate network
polyurethane by cross-linking a star cyclocarbonate with a
bi-functional amine oligomer having a functionality of at least
about 2.
77: A method of preparing a foam star nonisocyanate network
polyurethane, comprising the steps of: a) cross-linking a star
cyclocarbonate with a bi-functional amine oligomer having a
functionality of at least about 2; and b) adding a blowing
agent.
78: The method of claim 77, wherein the blowing agent is
pentane.
79: A method of preparing a star cyclocarbonate oligomer,
comprising the step of: reacting about x moles of a primary diamine
with about y moles of a cyclocarbonate oligomer in at least one
step to form a star cyclocarbonate oligomer of increased
functionality, wherein x.gtoreq.1, y.gtoreq.2, y>x.
80: The method of claim 79, wherein the star cyclocarbonate
oligomer is formed by reacting about 1 to about 2 moles of primary
diamine with about 2 to about 3 moles of the compound of the
formula depicted in FIG. 9, wherein R=H, CH.sub.3 or
C.sub.2H.sub.5, R'=CH.sub.2Cl or CH.sub.3, n=1, 2 or 3 and m1, m2
and m3 are independently selected over the range from 3 to 12
inclusive such that the molecular weight of the star cyclocarbonate
oligomer is about 600-1600.
81: The method of claim 79, wherein the primary diamine is selected
from the group consisting of substantially linear aliphatic primary
diamines, primary diamines comprising alicyclic groups, and
mixtures thereof.
82: A method of preparing a star epoxy ologomer comprising the step
of: reacting a total of about x moles of a primary diamine with y
moles of an epoxy oligomer in at least one step to form a star
epoxy oligomer of increased functionality, wherein x.gtoreq.1,
y.gtoreq.2, y>x.
83: The method of claim 82, wherein the primary diamine is selected
from the group consisting of substantially linear aliphatic primary
diamines, primary diamines comprising alicyclic groups, and
mixtures thereof.
84: A method of preparing a star aminohydroxyurethane oligomer
comprising the step of: reacting a star cyclocarbonate oligomer
with a primary diamine.
85: The method of claim 84, wherein the primary diamine is selected
from the group consisting of substantially linear aliphatic primary
diamines, primary diamines comprising alicyclic groups, and
mixtures thereof.
86: An acrylic cyclocarbonate oligomer, comprising: an acrylic
polymer with at least two pendant cyclocarbonate groups.
87: An acrylic oligomer selected from the group consisting of
acrylic hydroxyurethane oligomers and acrylic aminohydroxyurethane
oligomers.
88: An acrylic nonisocyanate network polyurethane.
89: The acrylic nonisocyanate network polyurethane of claim 88,
comprising an acrylic cyclocarbonate oligomer cross-linked with a
bi-functional amine having a functionality of at least about 2.
90: The acrylic nonisocyanate network polyurethane of claim 88,
wherein the network polyurethane is in the form of a foam or a UV
stable coating.
91: A paint or coating composition containing the acrylic
nonisocyanate network polyurethane of claim 88.
92: A method of synthesizing an acrylic nonisocyanate network
polyurethane by cross-linking an acrylic cyclocarbonate with a
bi-functional amine oligomer having a functionality of at least
about 2.
93: A method of preparing a foam acrylic nonisocyanate network
polyurethane comprising the steps of: a) cross-linking an acrylic
cyclocarbonate with a bi-functional amine oligomer having a
functionality of at least about 2; and b) adding a blowing
agent.
94: The method of claim 93, wherein the blowing agent is
pentane.
95: A method of preparing an acrylic cyclocarbonate oligomer
comprising the step of: reacting an acrylic epoxy resin with carbon
dioxide in the presence of a catalyst.
96: A method of preparing an acrylic amino-hydroxyurethane oligomer
comprising the step of: reacting an acrylic cyclocarbonate oligomer
with a primary diamine.
97: The method of claim 96, wherein the primary diamine is selected
from the group consisting of substantially linear aliphatic primary
diamines, primary diamines comprising alicyclic groups, and
mixtures thereof.
Description
FIELD OF THE INVENTION
[0001] The present invention generally relates to the preparation
of oligomeric cyclocarbonates and their use in nonisocyanate
polyurethanes (NIPU) and hybrid nonisocyanate polyurethanes
(HNIPU). In particular, the present invention relates to an
improved method of and apparatus for synthesis of oligomeric
cyclocarbonates from epoxy compounds and carbon dioxide. The
present invention further relates to the novel star and acrylic
cyclocarbonate compounds and their use in novel star and acrylic
hydroxy urethane oligomers and novel star and acrylic NIPU and
HNIPU compositions.
BACKGROUND OF THE INVENTION
[0002] Nonisocyanate polyurethane materials differ completely, both
in structure and in properties, from polyurethanes produced from
isocyanate containing oligomers and/or starting materials.
[0003] Prior art methods of producing polyurethane compounds that
rely upon the reaction of terminated hydroxyl groups with
terminated isocyanate groups requires the use of toxic starting
materials such as isocyanates and competing side-reactions during
production generates gases that result in an undesirable highly
porous material. Furthermore, polyurethanes derived from
isocyanates have hydrolytically unstable chemical bond rendering
them highly susceptible to environmental degradation.
[0004] These problems can be overcome by making of a polyurethane
without the use of toxic isocyanates, thus creating a modified
polyurethane with lower permeability and increased chemical
resistance properties to aqueous solutions of acids and
alkalis.
[0005] We previously discovered and disclosed in U.S. Pat. No.
6,120,905 to Figovsky, the structure of hybrid nonisocyanate
polyurethane network polymers, composite formed therefrom, and
their synthesis. These polyurethanes are formed by a reaction of
cyclocarbonates with primary amine polyfunctional oligomers. Our
prior patented process carries out the cyclocarbonate-oligomer
synthesis in thin film reactor at a temperature of 65 to
105.degree. C., and at the pressure of about 6.0 to 8.5 atm for
about 190 to 330 minutes. The resultant product contains not only
terminated cyclocarbonate-groups but also terminated epoxy groups.
We have subsequently found this process to have a very small
capacity and yields cyclocarbonate-oligomer with yellow color,
which is not suitable for use with clear coats and other products
requiring a clear or white color.
[0006] Urethane oligomers can be prepared, as shown in U.S. Pat.
No. 5,175,231 to Rappoport et al., by reacting a compound
containing a plurality of cyclocarbonate groups with a diamine
where the amine groups have different reactivities with
cyclocarbonate, so as to form urethane oligomer with amine
terminated groups. The amino-oligomer is used as a hardener of
epoxy resin and can be cross-linked by reacting it with an epoxy
resin to form a network structure. The cyclocarbonates are
synthesized from epoxy resins and carbon dioxide in the presence of
catalyst in a reactor under pressure 130-150 psi (8.9-10.3 bar) and
elevated temperature 240.degree. F. (150.degree. C.). In the
Rappoport et al. process, carbon dioxide is introduced in the
bottom of the reactor previously loaded with epoxy compound and
catalyst. The conversion of epoxy groups to cyclocarbonate groups
is strongly dependent upon the saturation of the epoxy compound by
the carbon dioxide. In the Rappoport et al process, despite
vigorous stirring that generates a foam, the reaction still takes
several hours and requires the use of high temperatures, high
pressures, large amounts of catalyst and long reaction times, to
avoid having a significant amount of unreacted epoxy groups that
reduce the concentration of the urethane groups and the number of
hydrogenated links in the final polyurethane network.
Unfortunately, although Rappoport et al. are able to ensure that
nearly all the epoxy groups have been turned into cyclocarbonate
groups in this reaction, they also end up producing undesirable
side reactions and products, while being more expensive and
time-consuming.
[0007] Other efforts to create such nonisocyanate polyurethanes
have had further problems. U.S. Pat. No. 4,758,615 to Engel Dieter,
et al. discloses the process of synthesis of polymers containing
nonisocyanate urethane groups by reacting polyamino compounds with
polycarbonates and reacting the reaction product further with
polycarboxylic acids for preparing aqueous polymer dispersions.
[0008] Production of other nonisocyanate polyurethanes based on the
reaction between the oligomeric bifunctional cyclocarbonate
oligomers and amines are disclosed by U.S. Pat. No. 5,340,889 to
Crawford et al. In this process, liquid hydroxyurethane products
are prepared by reacting a molar excess of bis-carbonate of a
bis-glycidyl ether of neopentyl glycol or
1,4-cyclo-hexanedimenthanol with polyoxyalkylenediamine. However,
the resultant polyurethanes lack a cross-linked network structure,
and thus are not chemically resistant and also are not suitable for
construction and structural materials.
[0009] The reaction of cyclocarbonates with amine compounds can
result in products other than polyurethanes. For example, USSR
Inventors Certificate No. 1353792 to Danilova, et al. discloses
reacting an epoxy-cyclocarbonate resin, urea formaldehyde, triazine
resin and amine hardener to prepare an adhesive composition. And
U.S. Pat. No. 4,585,566 to Wollenberg discloses the process of
synthesis of dispersants by reaction of a primary or secondary
amino group with mono-cyclic carbonate.
[0010] The tensile strength and deformation properties of
nonisocyante polyurethanes are comparable with standard isocyanate
polyurethanes, but the nonisocyanate polyurethanes do not have
pores, and thus are not sensitive to moisture in the surrounding
environment. The main properties of nonisocyanate polyurethanes
depend on the structure and the functionality of the cyclocarbonate
and amine oligomers from which it is made.
[0011] As noted above, the known reactions for preparing
nonisocyanate polyurethanes by using cyclocarbonates and primary
amines are problematic in that the reaction stops before the
process is completed resulting in an incompletely hardened network
polymer that adversely affects the properties of network polymer.
Although attempts have been made to prepare and add hardeners for
epoxy resin, such as shown in U.S. Pat. No. 5,175,231, they have
not is been successful in increasing the desirable properties of
the nonisocyanate polyurethanes.
[0012] The preparation of cyclocarbonates has also been fraught
with difficulties and products unsuitable for use in further
processing into nonisocyanate polyurethanes. For example the
process disclosed in U.S. Pat. No. 5,817,838 to Grundler et al.
prepares cyclocarbonates from epoxides and carbon dioxide in the
presence of a quanternary ammonium or phosphonium salt with a
further silver salt catalyst to assist the reaction process.
However, the use of the silver salt catalyst results in a material
that is unacceptably dark in color.
[0013] Other processes for the preparation of cyclocarbonates
require the use of high reactor temperatures despite the use of
various types of catalysts. For example, U.S. Pat. No. 5,153,333
uses quaternary phosphonium compounds as a catalyst, but still
requires reactor temperatures of 200.degree. C. U.S. Pat. No.
4,835,289 uses alkali iodides and reactor temperatures of
180.degree. C.
SUMMARY OF THE INVENTION
[0014] The present invention is directed to an improved method of
synthesis of oligomeric cyclocarbonates from digomeric epoxides and
carbon dioxide in the presence of a catalyst in a reactor or
cascade of reactors and the apparatus therefore. The improved
method allows the reaction to progress to completion at low
temperatures and low pressures for short time periods without side
reactions and the production of byproducts.
[0015] The invention is further directed to NIPU and HNIPU with
improved properties and the compositions from which they are
produced.
[0016] In particular, the invention is directed to a highly
functionalized star epoxy compounds, star cyclocarbonates, star
hydroxy urethane oligomers, and star NIPU and HNIPU, as well as to
and their method of preparation.
[0017] The present invention is also directed to an acrylic epoxy
compounds, an acrylic polymer with pendant cyclocarbonate groups,
an acrylic backbone hydroxy urethane oligomers, and acrylic
backbone NIPU and HNIPU and their methods of preparation.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1A is a schematic representation of a turbine mixing
device reactor in which the improved method of the present
invention is conducted;
[0019] FIG. 1B is a cross section of the turbine mixer blade of
FIG. 1 taken on line 1B;
[0020] FIG. 2A is a schematic representation of one embodiment of
the reaction to produce network nonisocyanate polyurethanes
(NIPU):
[0021] FIG. 2B is a schematic representation of another embodiment
is of the reaction to produce NIPU;
[0022] FIG. 3 is a schematic representation of an embodiment of the
reaction to produce hybrid network nonisocyanate polyurethanes
(HNIPU);
[0023] FIG. 4 is a schematic representation of an embodiment of the
reaction to produce hydroxyurethane oligomer with increased
functionality (HUOIF);
[0024] FIG. 5 is a schematic representation of another embodiment
of the reaction to produce epoxy oligomer with increased
functionality (EOIF);
[0025] FIG. 6 is a schematic representation of another embodiment
of the reaction to produce aminohydroxyurethane oligomer with
increased functionality (AHUOIF);
[0026] FIG. 7 is a Table showing the results of Examples 1-6 as
compared to the prior art;
[0027] FIG. 8 is a Table showing the network polyurethane
properties of Examples 7-9 relative to a control and to the prior
art; and
[0028] FIG. 9 depicts the formula for a reactant used to make a
cyclocarbonate terminated "star" oligomer of increased
functionality.
DETAILED DESCRIPTION OF THE INVENTION
[0029] The synthesis of nonisocyanate network polyurethanes and
hybrid nonisocyanate network polymers involves a number of stages.
The first stage is the preparation of a cyclocarbonate from the
reaction of an epoxy or epoxide with carbon dioxide. The resultant
cyclocarbonate is reacted with an amine containing compound to form
an hydroxy urethane oligomer. The hydroxy urethane oligomer is then
cross linked to form a nonisocyanate network polyurethane (NIPU) or
a hybrid nonisocyanate network polyurethane (HNIPU). The properties
of the resultant NIPU or HNIPU depend upon the properties of the
cyclocarbonate and amine oligomers from which it is produced.
[0030] Others in the art have had problems with obtaining NIPU and
HNIPU with the desired properties due to many factors, including
the problems with obtaining a cyclocarbonate material of sufficient
purity.
[0031] Accordingly, the present invention is directed to an
improved method and apparatus for the preparation of
cyclocarbonates from epoxides and epoxy containing compounds by
reaction with carbon dioxide. The invention is further directed to
the preparation of novel highly functionalized star cyclocarbonate
and novel acrylic backbone polymers with pendant cyclocarbonate
groups and the use of such novel compounds in the preparation of
novel hydroxy urethane oligomers and novel NIPU and HNIPU
compositions.
[0032] In prior reaction systems, as described above, carbon
dioxide is introduced into the bottom of a reactor vessel and
reacts with the epoxide as it upwardly traverses the reaction mass.
To ensure that the reaction proceeds, it is necessary to use high
pressures of carbon dioxide, as well as high temperatures, long
reaction times, and catalysts. All of these degrade the resultant
product requiring separation and purification steps before the
cyclocarbonate product can be used.
[0033] The improved process of the present invention utilizes a
reactor that maximizes the surface contact area between the
reactionary epoxide mass and the carbon dioxide, thus obviating the
need for high temperatures, high pressures, and long reaction
times. In the process of the present invention, the saturation of
reaction mass by carbon dioxide is maximized by both feeding the
carbon dioxide to the head space above the reaction mixture and
feeding the carbon dioxide directly into the reaction mass by means
of a turbine mixing device with a gas entrainment impeller.
[0034] The process can best be understood by reference to FIG. 1A,
which shows a reaction vessel 5 having a diameter d.sub.3 in which
the epoxide is charged to form reaction mass 1 having a height
H.sub.1. Carbon dioxide is introduced by means of inlet 4 into the
head space above the reaction mixture 1. Carbon dioxide is also fed
by means of a gas turbine mixer which comprising a hollow shaft 3
in fluid communication with hollow gas entrainment impeller 6 that
feed the carbon dioxide by means of gas outlets 7 directly into the
reaction mixture 1 while rotating. The hollow shaft 3 has an inside
diameter of d.sub.2 and contains inlet ports of openings 2, each
with a diameter of d.sub.4, that permit the carbon dioxide gas to
continuously recirculate from the head space above the reaction
mass 1 directly into the reaction mass 1. The carbon dioxide gas
enters near the top of the hollow shaft 3 through openings 2 and is
drawn through the hollow shaft 3 and through hollow gas entrainment
impeller 6 having a height H.sub.2 and is then the expelled through
dispersion ports or outlets 7 located at the tip of the impeller 6.
The dispersion ports or outlets each have a diameter of d.sub.5.
The diameter of the impeller 6, as measured from tip to tip, is
denoted by d.sub.1. The impeller is located a distance h from the
bottom of the reactor 5. The rotation of the impeller 6 creates a
vacuum at the tip of impeller where the dispersion ports or outlets
7 are located. The speed of rotation is directly related to the
vacuum created, and thus the driving force for the dispersion of
the carbon dioxide gas into the reaction mass 1, with the higher
the speed, the higher the vacuum, and the higher the driving
force.
[0035] In a preferred embodiment of the invention, the ratio of the
inside diameter d.sub.2 of shaft 3 to the largest diameter d.sub.1
of the turbine mixing device measured from tip of impeller to tip
of impeller as shown in FIG. 1B is preferably in the range of about
1:4 to about 1:6, with a range of 1:4 the most preferred.
[0036] In another preferred embodiment, the ratio of the sum of the
square of the diameter d.sub.4 of the inlet ports 2 on the hollow
shaft 3 to the sum of the square of outlet ports d.sub.5 as shown
in FIG. 1B is preferably from about 1:3 to about 1:4.
(.SIGMA.d.sub.4:.SIGMA.d.sub.5 FIG. 1).
[0037] In yet another preferred embodiment of the invention, the
ratio of the height H.sub.2 of impeller 7 to the height H.sub.1 of
mixing layer or reaction mass 1 is preferably from about 1:2 to
about 1:4.
[0038] The synthesis of cyclocarbonates can be carried out in a
single reactor in a batch wise process or in a series or cascade of
reactors on a continuous action basis. When a cascade of reactors
is used, a cyclocarbonate product of extremely great purity can be
obtained.
[0039] The reaction is conducted in the presence of a suitable
catalyst, which are well-known to those of skill in the art, and
include quaternary ammonium salts, quaternary phosphonium salts,
quaternary arseniurm salts, alkali metal halides of Cl, Br, I, and
the like.
[0040] The reaction is preferably conducted at a temperature of
about 70-180.degree. C. and a pressure of at least one atmosphere,
preferably from about 1-15 bar. For a clearer product, lower
temperatures are preferred.
[0041] This reaction system has unexpectedly been found to have
excellent gas-liquid contact without the generation of foam.
Furthermore, due to the excellent gas-liquid contact made in this
reactor, the reaction time is greatly reduced, generally by a
factor of 2 to 4, over other known systems. For example, under
identical conditions of temperature and pressure, the present
system requires only 40 to 120 minutes for reaction, while that
shown in U.S. Pat. No. 5,175,231 requires at least a time period of
180 minutes.
[0042] We have also found that this reaction system permits a
gentle reaction without the use of harsh conditions that result in
the production of undesired byproducts and side reactions.
[0043] The present invention further relates to the preparation of
novel network nonisocyanate polyurethanes using the novel
synthesized cyclocarbonates of the present invention. In one
embodiment of the invention, the novel synthesized cyclocarbonates
are star carbonates of increased functionality. In another
embodiment, the novel synthesized cyclocarbonates are acrylic
polymers with pendant cyclocarbonate groups.
[0044] Functionality, also referred to as "f", refers to the number
of reactive centers and is calculated from the structural formula.
Thus, an epoxy terminated oligomer would have two epoxy groups, and
thus a functionality of 2. If it is reacted in accordance with the
present invention as shown in FIG. 5, the resultant star epoxy
oligomer would have a functionality of 4.
[0045] The star oligomers of the present invention refer to
oligomers is with multiple functional groups that have been linked
together using one functional group from each oligomer to form a
linkage, such as an hydroxyurethane linkage, to form a polymer with
increased functionality. This linkage process can be used to create
a star polymer of any desired functionality. Generally a
functionality of about 2 to about 6 is preferred, and more
preferably about 3 to about 5, as too great of an increase in
functionality can hinder the use of the star oligomer in
preparation of desired products such as network nonisocyante
polyurethanes.
[0046] For example, a star-epoxy oligomer is a product of the
reaction between an oligomer with terminated epoxy groups (by
functionality not less than 1.99) and amino oligomer with primary
amino groups (by functionality no less than 1.99) so that one
terminated epoxy group from one oligomer and one terminated epoxy
group from another oligomer both react with the amino oligomer to
form an hydroxyurethane linkage connecting the two epoxy oligomers
together to form a star epoxy oligomer. See for example FIG. 5
which shows the reaction of 4 epoxy oligomers to form a star epoxy
oligomer of functionality 4, i.e. 4 unreacted epoxy groups
remaining.
[0047] In one embodiment of the invention, the network
nonisocyanate polyurethanes (NIPU) of this invention are prepared
by an improved method by interaction in situ of at least one
cyclocarbonate hydroxyurethane "star" oligomer (star cyclocarbonate
oligomer) with increased functionality (f.gtoreq.3) and having
terminated cyclocarbonate groups and at least two hydroxyurethane
linkage groups with amino-oligomer containing at least two
terminated primary amino groups with at least two hydroxyurethane
groups. See FIG. 2A.
[0048] In another embodiment of the invention, the network
nonisocyanate polyurethanes are prepared by interaction of "star"
oligomer with terminated amino groups (FIG. 6) with oligomer
containing epoxy groups. (functionality f.gtoreq.2). The network
hybrid nonisocyanate polyurethanes are prepared. See FIG. 2B.
[0049] In another embodiment of the invention, the network
nonisocyanate polyurethanes are prepared by interaction of "star"
oligomer with terminated amino groups (FIG. 6) and epoxy oligomer
with increased functionality (EOIF) (FIG. 5).
[0050] In another embodiment of the invention, "star"
hydroxyurethane oligomer with increased functionality (HUOIF) is
synthesized by reacting n moles of oligomer, containing terminated
cyclocarbonate groups (functionality.gtoreq.3), and m moles of
amines, wherein n>m. See FIG. 4.
[0051] In another embodiment of the invention, "star"
hydroxyurethane oligomer with increased functionality (HUOIF) is
synthesized by reacting n moles of oligomer, containing terminated
cyclocarbonate groups (functionality.gtoreq.3), and m moles of
amines, where n>m. See FIG. 5.
[0052] In another embodiment of the invention, "star" hydroxylamino
oligomer with increased functionality (AHUOIF) with terminated
amino groups is synthesized by interaction of n moles of HUOIF
(functionality f.gtoreq.3) and m moles of primary diamines where
m.gtoreq.f. See FIG. 6.
[0053] In a further embodiment of the invention, the star polymers
are multi or polyfunctional polymers can contain a multiplicity of
different types of functional groups. For example, the star epoxy
oligomer may have epoxy, cyclocarbonate, amine and other groups,
not just the epoxy groups.
[0054] In yet another embodiment of the invention, acrylic epoxides
in the form of an acrylic backbone polymers with pendant epoxide
groups, are used to produce novel acrylic cyclocarbonate oligomers.
The novel acrylic cyclocarbonate oligomers are reacted with primary
amines, diamines and tertiary amines to form a novel acrylic
aminohydroxyurethane that can be cured to form an acrylic NIPU or
HNIPU. Polyfunctional acrylic oligomers known to those skilled in
the art can be used in the present invention. For example,
copolymers of acrylic monomers methylmethacrylate, butylacrylate,
1-methacrylate-2,3-epoxy, and the like can be used. An example of
such a polyfunctional acrylic oligomer is 1
[0055] The novel star and acrylic NIPU and HNIPU compositions of
the present invention can take any suitable form and the oligomers
from which it is made can be selected to provide the desired
properties such as gloss, degree of hardness, flexibility, UV
stability, abrasion resistance, weathering resistance and the like.
From this disclosure, one of skill in the art would be able to make
an appropriate selection of materials without undue
experimentation.
[0056] Due to their superior structure and excellent resistance to
degradation, the novel star and acrylic NIPU and HNIPU compositions
of the present invention are useful for numerous applications
including crack resistant composite materials, chemically resistant
coatings, sealants, glues, paints and the like. These novel
compositions are useful in a host of industries. For example, uses
in the automotive industry include bumpers, dashboards, inhibiting
sealants, paints, plastics, repair putty, seating, steering wheels,
trim components, truck beds, and the like. Aerospace uses include
airplane and rocket sealants, interior components, seating,
syntactic non-burning foam, and the like. Uses in the construction
industry are myriad and include adhesives, coatings, coverings,
crack barrier concrete, elastomers, epoxy resin hardeners, exterior
wallboard, flooring, foams, glues, metals, plastics, plywood,
rooftops, sealants, wood coatings, and the like. Industrial uses
include coatings, paints and sealants for heavy industrial
equipment, machinery, molded parts, and the like. The novel
compositions are particularly well suited for marine environments
and can be used for bridge decks, coatings, interior and exterior
components, paints, sealants and the like. Other possible uses
include appliances, footwear, furniture, plastics, synthetic
leather, toys, and the like.
[0057] These novel compositions are particularly useful as coatings
and paints and can be used as coatings on industrial machines, as
floor coatings, as coatings and paints for automobiles, trucks, and
buses, as coatings and paints on outdoor structures such as bridges
and trusses, as coatings and paints on interior structural members
such as trusses, ceilings, walls, and the like.
[0058] By selection of the oligomers used in preparation of these
novel compositions, one skilled in the art can provide a liquid
paint or coating composition containing these novel compositions
that is sprayable with conventional paint equipment, has a potlife
of sufficient time, has reduced VOC, and suitable cure times. The
resultant cured coatings have a desired gloss, hardness, adhesion,
impact resistance, corrosion resistance, humidity resistance,
chemical resistance, and weathering resistance.
[0059] In a further embodiment of the present invention, these
novel star and acrylic NIPU and HNIPU compositions can be foamed
using a blowing agent such as pentane to provide a foamed coating
composition.
[0060] The present invention provides structures, which solve the
problem of increasing of the mechanical properties of NIPU and
HNIPU.
[0061] Since the present reaction does not require the use of
highly toxic materials, it is possible to perform the reaction
without special equipment.
[0062] In general, the synthesis of nonisocyanate network
polyurethanes of the present invention is conducted as follows:
[0063] The First Stage.
[0064] Any suitable epoxy compound known to one skilled in the art
can be reacted with carbon dioxide to form the corresponding
cyclocarbonates. The reaction can be conducted in either a
batch-process (single reactor) or in a continuous process (cascade
or series of reactors) in the presence of a suitable catalyst
well-known to those of skill in the art. Examples of suitable
catalysts include quaternary ammonium salts, quaternary phosphonium
salts, quaternary arsenium salts, alkali metal halides (Cl, Br, I)
and the like of alkali metal. In a preferred embodiment of the
invention, the reactor temperature is 70-180.degree. C. and
pressure 1-15 bar is supported.
[0065] The carbon dioxide is fed to the upper part of the reactor,
from which it is fed by the turbine mixing device (gas entrainment
impeller) directly in to the reactionary mass.
[0066] Due to the dispersion effects of the turbine mixing device
which result in a "soaking up" of the carbon dioxide by the
reactionary mass, the carbon dioxide is entered into the
reactionary mix throughout the entire working volume of the
reactionary mass and thus raises saturation of epoxy compounds by
the carbon dioxide enabling the reaction to be completed in a
significantly shorter time than in the prior art devices utilizing
periodic action under pressure. It provides faster and complete
production of cyclocarbonate, with the reaction of the present
invention being 2 to 4 times faster than that in the prior art.
EXAMPLE 1
[0067] A reactor of the type depicted in FIG. 1 is used to
efficiently prepare cyclocarbonates.
[0068] 500 grams of epoxy resin D.E.R.-324 (Dow Chemical) were
mixed with the catalyst tetrabutylammonium bromide (C.sub.4H.sub.9)
.sub.4NBr in quantity 0.5% of weight of epoxy and loaded into the
reactor (volume--1 liter). Carbon dioxide was fed for a period of
45 minutes through the hollow shaft and out the holes at the ends
of the impeller into the epoxy/catalyst mixture. The initial
reactor conditions were a temperature of 70.degree. C., and a
pressure of 8 bar, at which point absorption of the carbon dioxide
commenced. The reaction was exothermic, and finished at a
temperature of 120.degree. C. The mean velocity of absorption
CO.sub.2 during the reaction was 2.4 grams per minute.
[0069] The reaction resulted in the preparation of 580 grams of a
cyclocarbonate oligomer containing 35% cyclocarbonate groups and
0.3% epoxy groups. Conversion was 99%.
EXAMPLE 2
[0070] Using the procedure of Example 1, 620 grams epoxy resin
Oksilin-6B (Russia) were mixed with the catalyst tetrabutylammonium
bromide (C.sub.4H.sub.9) .sub.4NBr in quantity 0.5% of weight of
epoxy and loaded into the reactor (volume--1 liter). Carbon dioxide
was fed to the reactor for a period of 40 minutes through the
hollow shaft and out of the holes in the impeller into the
epoxy/catalyst mixture. The initial reactor conditions were a
temperature of 70.degree. C. and a pressure of 8 bar, at which
point absorption of the carbon dioxide commenced. The reaction is
exothermic and at the completion thereof the temperature was
120.degree. C. The mean velocity of absorption CO.sub.2 during the
reaction was 1.7 grams per minute.
[0071] The reaction resulted in the preparation of 580 grams of
cyclocarbonate oligomer containing 22.7% cyclocarbonate groups and
0.1% epoxy groups. Conversion was 99%.
EXAMPLE 3
[0072] Using the procedures of Example 1, 523 grams of epoxy resin
D.E.N.-431 (Dow Chemical) were mixed with the catalyst
tetrabutylammonium bromide (C.sub.4H.sub.9) .sub.4NBr in quantity
0.5% of weight and the epoxy/catalyst mixture was loaded to the
reactor (volume--1 liter). The carbon dioxide was fed to the
reactor under a pressure of 8 bars for a period of 90 minutes. The
initial temperature of the reactor was 70.degree. C. and the final
temperature increased to 120.degree. C. due to the exothermic
nature of the reaction. The mean velocity of absorption of CO.sub.2
during the reaction was 2 grams/min.
[0073] The reaction resulted in the preparation of 590 grams of
cyclocarbonate oligomer containing 28% cyclocarbonate groups and 1%
epoxy groups. Conversion was 97%.
EXAMPLE 4
[0074] Using the procedure of Example 1, 516 grams of epoxy resin
D.E.R.-324 (Dow Chemical) was mixed with the catalyst
tetrabutylammonium iodide (C.sub.4H.sub.9) .sub.4NI in quantity of
0.5% of weight of epoxy. The epoxy/catalyst mixture was then loaded
into the reactor (volume--1 liter). Carbon dioxide was fed to the
reactor through the hollow shaft and out of the impeller at a
pressure of 1.5 bar for a period of 40 minutes. The initial
temperature of the reactants was 70.degree. C. and increased due to
the exothermic nature of the reaction to a final temperature of
120.degree. C. The mean velocity of absorption CO.sub.2 during the
reaction was 2.8 grams/min.
[0075] The reaction resulted in the preparation of 580 grams of
cyclocarbonate oligomer containing 34% cyclocarbonate groups and
0.5% epoxy groups. Conversion was 98%.
EXAMPLE 5
[0076] Using the procedure of Example 1, 516 grams of epoxy resin
D.E.R.-324 (Dow Chemical) were mixed with the catalyst
tetrabutylammonium chloride (C.sub.4H.sub.9) .sub.4NCl in quantity
0.5% of weight of epoxy. The epoxy/catalyst mixture was then loaded
into the reactor (volume--1 liter). Carbon dioxide was fed to the
reactor at atmospheric pressure for a period of 120 minutes. The
initial reactor temperature was 70.degree. C. increased to
120.degree. C. due to the exothermic nature of the reaction.
[0077] The reaction resulted in the preparation of 500 grams of
cyclocarbonate oligomer containing 34% cyclocarbonate groups and
0.3% epoxy groups. Conversion was 98%.
EXAMPLE 6
[0078] Using the procedure of Example 1, 600 grams of epoxy resin
Laproxide (Russia) were mixed with the catalyst tetrabutylammonium
bromide (C.sub.4H.sub.9) .sub.4NBr in the quantity 0.5% of weight
of epoxy. The epoxy/catalyst mixture was then loaded into the
reactor (volume--1 liter). Carbon dioxide was fed to the reactor at
a pressure of 1.5 bar for a period of 90 minutes. The initial
temperature of the reactor was 70.degree. C. and increased to a
final temperature of 120.degree. C. due to the exothermic nature of
the reaction.
[0079] The reaction resulted in the preparation of 665 grams of
cyclocarbonate oligomer containing 23% cyclocarbonate groups and
0.3% epoxy groups. Conversion was 98%.
[0080] The conversion rates and reaction information of examples
1-6 are summarized in the Table of FIG. 7 and compared with the
results obtained using the procedures set forth in U.S. Pat. No.
5,175,312.
[0081] Network nonisocyanate polyurethanes were prepared using the
synthesized cyclocarbonates.
[0082] The Second Stage.
[0083] In the second stage of the reactor, a cyclocarbonate or an
epoxy is oligomer is reacted with amino containing compound, in
particular a compound containing terminated amino groups, to form
"star" hydroxyurethane or epoxy oligomers with increased
functionality (FIG. 5-7).
[0084] Suitable terminated amino groups are those containing
primary amino groups, i.e. --NH.sub.2 groups without radicals. In
particular, polyfunctional primary amino-terminated oligomers of
the following formula may be used:
R--(NH.sub.2).sub.m
[0085] wherein
[0086] R is aliphatic, cycloaliphatic, ether, ester and acrylic
groups, and m is.gtoreq.3.
[0087] Any cyclocarbonate or epoxy oligomer can be used in this
reaction. In a preferred embodiment of the invention, the
cyclocarbonate and epoxy oligomers are cyclocarbonate or epoxy
oligomers of increased functionality having at least two and
preferably more functional groups in their structure. In a
preferred embodiment of the invention, the functionality is from
about 3 to about 5, and is more preferably from about 3 to about
4.
[0088] In one embodiment of the invention, a cyclocarbonate
oligomer with three terminal cyclocarbonate groups reacts with
primary diamine as shown on the FIG. 5 to form "star" oligomer with
four or more cyclocarbonate and hydroxyurethane groups. The
oligomer with two terminated epoxy groups reacts with primary
diamine as shown on the FIG. 6 to form "star" oligomer with four or
more epoxy groups. On the base of "star" oligomers with increased
functionality amino adducts were prepared (FIG. 7).
[0089] The diamines used in the present invention have amine groups
with equal or different reactivities. The oligomer with increased
functionality has at least average three amino groups.
[0090] The Third Stage.
[0091] The resulting urethane containing "star" oligomer can serve
as a hardener for oligomers with epoxy or cyclocarbonate groups. Or
"star" oligomer with terminated cyclocarbonate groups which may be
cured by primary amino oligomer (f>,=2). So we have a material
(the urethane containing "star" oligomers with amino end groups,
cyclocarbonate end groups and epoxy end groups with increased
functionality) that, have the substantial advantages over the prior
art it has the increased strength and elasticity.
[0092] Any cyclocarbonate or epoxy oligomer may be used.
[0093] The practical applications of this invention are very
interesting. For example, we can produce paints, adhesives,
composite compounds, etc.
[0094] The present invention provides a material that has
combination is of all the advantage of known nonisocyanate
materials plus increased mechanical properties of polyurethane.
EXAMPLE 7
[0095] Stage II
[0096] "Star" cyclocarbonate oligomer containing hydroxyurethane
groups with increased functionality was prepared by dissolving of
2M (2268 g) of cyclocarbonate oligomer Laprolat-803(Example 6) in
1M (170 g) of Isophorondiamine (CREANOVA spezialchemie GmbH). This
2438 g were charged into the reactor, which is jacketed for
temperature control. The reactor was operated at atmospheric
pressure and in several small portions, because the reaction is
exothermic. The reaction is going at 80.degree. C. during 3-4
hours.
[0097] It is also possible to prepare oligomers in presence of
solvents. It is possible to use any of diamine and cyclocarbonate
compound. After all the amine was added to the reactor samples were
taken and measured for amine group concentration. The content of
amine group in the finished product was about 0%, indicating that
amine groups had reacted with cyclocarbonate groups and we have now
new "star" hydroxyurethane oligomer with increased functionality
(HUOIF).
[0098] Stage III
[0099] The urethane containing "star" oligomer from the stage I was
reacted with Isophorondiamine (ISPhDA) and resulted in the
formation of an elastomer with a tensile strength 1.5 Mpa and an
elongation at break of 250% as measured by ASTM D638884.
EXAMPLE 8
[0100] Stage II
[0101] "Star" cyclocarbonate oligomer with increased functionality
was prepared by dissolving of 3M of cyclocarbonate oligomer (3402
g) Laprolate-803 (Example 6) in 2M of isophorondiamine (Creanova
specialchemie GmbH) -340 g. This 3742 g were charged into the
reactor. The process is as stage 1 (Example 7).
[0102] Stage III
[0103] The urethane containing oligomer from the stage I was
combined with Isophorondiamine (ISPhDA) to form elastomer with
Tensile strength 0.7 Mpa and Elongation at break 300%.
EXAMPLE 9
[0104] Stage II
[0105] "Star" cyclocarbonate oligomer with increased functionality
(CCOIF) was used from stage 1 (Example 7) for preparing "star"
amino containing hydroxyurethane oligomer with increased
functionality (AHUOIF).
[0106] AHUOIF was prepared by dissolving of 1M (2438 g) CCOIF from
the stage 1 (Example 7) in 8M (1360 g) ISPhDA. The reactor was
operated at atmospheric pressure and into several small portions.
The reaction is going at 80.degree. C. during 2-3 hours. Total 3798
g. The "star" epoxy oligomer with increased functionality EOIF was
prepared by dissolving of 4M (1200 g) of Polypox R-14
(neopentylglycoldiglycidyl ether, UPPC GmbH) in 1M (170 g) of
ISPhDA. The reaction is going at 80.degree. C. during 1-2
hours.
[0107] Stage III
[0108] The urethane containing oligomer AHUOIF and epoxy oligomer
EOIF from stage I was combined with 8M (2400 g) Polypox R-14 to
form elastomer with Tensile strength 11 Mpa and Elongation at Break
90%.
EXAMPLE 10
[0109] Stage II
[0110] The AUOIF was used from stage I (Example 9).
[0111] The EOIF was used from stage I (Example 9).
[0112] Stage III
[0113] The urethane containing oligomer HUOIF and epoxy oligomer
EOIF from Stage I was combined with 4M (1200 g) of Polypox R-14 to
form elastomer with Tensile strength 9 Mpa and Elongation at Break
120%.
[0114] A comparison of the network polyurethane properties of
examples 7-10 are summarized in the Table 2 of FIG. 8 and compared
with the resultant polyurethane obtained using the procedures set
forth in U.S. Pat. No. 5,175,312.
EXAMPLE 11
[0115] Stage I
[0116] An acrylic cyclocarbonate oligomer was prepared using the
procedures and equipment of example 1, 425 grams of acrylic epoxy
resin Setalux 17-1433 (60%) (Akzo Nobel) was mixed with 0.25% by
weight of epoxy of a tetrabutlyammonium bromide catalyst
(C.sub.4H.sub.9)NBr. The epoxy/catalyst mixture was loaded into the
reactor (volume--1 liter). Carbon dioxide was fed under a pressure
of 8 bar for 180 minutes. The reaction began at 70.degree. C. and
due to the exothermic nature of the reaction ended at a temperature
of 120.degree. C.
[0117] The reaction resulted in the preparation of 447 grams of an
acrylic cyclocarbonate oligomer with 13% cyclocarbonate groups and
0.4% epoxy groups. Conversion was 96%.
[0118] Stage II
[0119] The amineurethane oligomer with increased functionality
(AUOIF) was prepared by dissolving 2M (1170 g) of cyclocarbonate of
Polypox R-20 (UPPC) previously synthesized in the reactor using the
procedures of Example 6 in 1M (170 g) of Isophorondiamine (Creanova
spezialchemie GmbH). The 1340 g mixture of cyclocarbonate in
diamine was charged into the reactor, which was jacketed for
temperature control. The reaction was conducted at 80.degree. C.
for 3 hours, during which an additional 8M (1326 g) of
Isophorondiamine was added. The reaction yielded 2700 g of
AUOIF.
[0120] Stage III
[0121] 669 g of the acrylic cyclocarbonate oligomer from stage I
and 225 g of the AUOIF from stage II were combined by stirring at
room temperature to form a liquid that was coated on a metal
substrate at a thickness of 50 mkm. The coated substrate was cured
for 2 hours at a temperature of 100.degree. C. to form a UV-stable
coating. The hardness of the cured coating was H, the impact (face)
was 50 kg.cm.
EXAMPLE 12
[0122] Stage III
[0123] 669 g of the acrylic cyclocarbonate oligomer from stage I of
Example 11 and 81 g of 100% Vestamine TMD (Creanova) were combined
by stirring at room temperature to form a liquid that was coated on
a metal substrate at a thickness of 50 mkm. The coated substrate
was cured for 2 hours at a temperature of 110.degree. C. to form a
UV-stable coating. The hardness of the cured coating was H, the
impact (face) was 50 kg.cm.
EXAMPLE 13
[0124] Stage II
[0125] A synthesis of a cyclocarbonate with a tertiary amine group
containing compound was conducted.
[0126] A cyclocarbonate based upon Eponex 1510 (Shell) was prepared
using the procedures and conditions of Example 6. 562 g of the
resultant cyclocarbonate was mixed with 146 grams of N,N-bis(3
aminopropyl)methylamine (BASF). The resultant cyclocarbonate/amine
mixture was charged into the reactor, which was jacketed for
temperature control. The reaction was conducted at 100.degree. C.
for a period of 2-3 hours and yielded 708 g of an amino containing
oligomer.
[0127] Stage III
[0128] The 708 g of the amino containing oligomer from stage II and
1340 (100%) acrylic epoxy resin Setalux 17-1433 were combined by
stirring at room temperature to form a liquid that was coated on a
metal substrate at a thickness of 50 mkm. The coated substrate was
cured for 1 hour at a temperature of 100.degree. C. to form a
UV-stable coating. The hardness of the cured coating was H, the
impact (face) was 50 kg.cm.
* * * * *